Improved confection



Patented cc. El, 235

novnn C Benjamin R. arris, Chicago, m.

No Bra. Application April 3, 1935, Serial No. 14,528

23 Claims. (on. 99-16) present application is a continuation in part, I

describe the use of esters of phosphoric acid formed by reacting alipoph'fle material having at least one free hydroxy group with aderivative of 0 phosphorus capable of forming an ester thereof, incertain types of confections to secure certain advantages andimprovements therein.

The reaction product of the lipophile material and the derivative ofphosphorus preferably is 15 neutralized, but it may be employed in anunneutralized condition.

The type of confection to which the invention relates is that wherein acomminuted material such as cocoa powder, powdered milk, sugar or .20thelike is combined with a fat. Examples of confections of this type arechocolate, chocolate-like coatings for candy, coatings for ice cream andcookies and other confections such as tofiees, caramels, icings,fillings, fudges, butter creams, and

25 other compositions of the same general class. In each of these typesof confections, a comminuted material including sugar and/or othersimilar substances such as cocoa powder, dried egg material, powderedmilk, and the like, are dispersed in the 30 fat, or otherwise combinedwith the fat.

Generally my present invention is in the nature of an improvement overthe process and product described in my prior patent by means of whichvery much improved results are ob- 5 tained, particularly in thereduction of viscosity of chocolate. Other advantages and improvementsalso flow from the new features incorporated in the process and productin addition to viscosity reduction. In general, I proceed in the 40 samemanner described in my prior application with the exception that apretreatment step is employed prior to the formation of the-phosphoricacid ester, the nature and efiect of which will be pointed out more indetail hereinafter. 45 For the convenience of those skilled in the art,I shall in general repeat the major portion of the disclosure of myprior application.

For an understanding of the problems and advantages of the presentinvention, reference may 50 be hadto so-called chocolate enrobing compositions. producing a chocolate enrobing composition having a suitableviscosity at a temperature at which the material can be convenientlyworked. Atten- 55 tion must also be given to retaining a suitable Herethere is a specific problem in viscosity for a sumcient period tofacilitate commercial manipulations. It is known that viscosities canoften be reduced by increasing the fat content, but in general thisparticular approach to the'problem is not satisfactory, as those skilledin the art understand. Similar problems exist in the manufacture and useof icings wherein powdered sugar and fat usually are employed.

In the manufacture of certain other confections, such as toffees,caramels, fudges, and the like, fatty ingredients are heated at a. hightemperature with comminuted solids, such as sugar.

in the presence of relatively small amounts of moisture, and, it isnecessary to have an emulsifying agent in order to maintain a stableemulsion at the high temperature. In the preparation of cooked toifee,for example, a temperature of about 285 F. is employed to reduce themoisture content of the syrup.

The principafobject of the invention is to improve confections of thegeneral character described.

Another object is the provision of a new ingredient for use incompositions of the character outlined.

Another object is to reduce thexviscosity of chocolate confections ofthe general character indicated by the incorporation therewithofrelatively small amounts of an improved addition substance.

A further object is the utilization of an imaction products of lipophilematerials having a free hydroxy group and a derivative of phosphoruscapable of forming-a phosphoric acid ester, the reaction productpreferably being subsequently neutralized. Some of the addition productsemployed are described in my co-pending application, Serial No. 705,825,filed January 8, 1934. I shall, however, describe my addition substancesmore in detail in a later part of the specification. It may be statedgenerally at this time, however, that these materials are in generalmodified lipins in that the reaction products contain a lipophile groupand a phosphate hydrophillic group. The amount of these materialsemployed is of the order of A to 3% on the basis of the fat used,although lesser and greater amounts can be employed if desired.

The character of improvement effected by the introduction of myinterface modifiers naturally varies with the composition of matter athand. For example, in a conventional chocolate mix, such as 148 parts ofpowdered sugar (6X cane sugar), 52 parts of cocoa powder (12% fatcontent), 100 parts of cocoa butter, and flavoring, the principalimprovement is a substantial reduction in viscosity. In a conventionaltoffee, for example, consisting of parts of cocoanut stearine, 140 partsof 4X sugar, 20 parts of invert sugar, and 20 parts of water, whereinthe mix is boiled at about 285 F., and the fat must emulsify and remainemulsified at this relatively high temperature, the improvement islargely one in the case of emulsification and the stability of theemulsion obtained. In still other preparations, additional improvementsare found such as in the character of texture, appearance, and/orflavor, but it is to be noted that in every instance, whatever thecharacter of the improvement at hand, the physical chemical mechanism isone of interface modification effected by the introduction of the classof interface modifiers which-I employ herein. I

The-interface modifiers of my invention may be described by referring tothe process of making them. In general, the preparation consistspreferably in reacting a more or less lipophile material with at leastone free .hydroxy group," for example, a diglyceride or a mixture ofdiglycerides with phosphorus pentoxide (or some other form or derivativeof phosphorus, such as metaphosphoric acid, pyro-phosphoric acid,phosphorus trioxide, phosphorus oxychloride, phosphorus pentachloride,ethyl metaphosphate, and other phosphorus reagents capable of formingesters of phosphoric acid), to yield an ester of phosphoric acid withhydrophile properties and with strong lipophile properties. Examples A,B, C, and D, .will serve to illustrate my general method for thepreparation of some of the interface modifiers with the use of which thepresent invention is concerned.

Example A 175 parts of refined deodorized cottonseed oil are heated with10 parts of glycerine (United States Pharmacopoeia grade) in an inert,that is, non-oxidizing atmosphere, with stirring, to about 200 C. .17parts of flaked caustic soda are then added with stirring, then raisedto about 250 C.

and maintained at this temperature with continuous stirring for abouttwo hours, and cooled to room temperature in an inert atmosphere.

45 parts of the above product, which consists essentially of a mixtureof diglycerides, and 3 parts of finely divided phosphorus pentoxide aremixed at a temperature of about 50 to 60 C., and then heated withvigorous stirring in a substantially dry, inert atmosphere to about toC., or, if desired, somewhat higher, and maintained at this temperaturefor two to three hours.

The reaction mixture is then allowed to remain at rest and to cool in aninert atmosphere. A small proportion of insoluble matter settles to thebottom of the container and while the mixture is still liquid, it ispoured off from the sediment. The decanted material may be used as suchor it is further chilled until it is semi-solid and plastic, and 50%aqueous sodium hydroxide solution is added gradually, with stirring, in

sufficient proportion to render the product preferably substantiallyneutral to litmus, though the product may be left slightly acid orfaintly alka-. line to litmus. The amount of sodium hydroxide solutionto be added is determined as follows:

A 2 gram sample'of the material to be neutralized is dissolved in about10 c. c. of neutral ethyl ether. 15 c. c. of neutral isopropyl alcoholare added and then 150 c. c. of distilled water are stirred in. Themixture is then titrated with normal sodium hydroxide solution, usingphenolphthalein as indicator. From this titration the amount of causticsoda solution required is computed.

The product obtained consists principally of esters of phosphoric acidin the form of a light colored, pasty material with valuable interfacemodifying properties along the lines discussed hereinabove.

The reaction with phosphorus pentoxide described herein under Example Ais susceptible to considerable variation as to the proportion ofphosphorus pentoxide used, the fineness thereof, the temperature, andthe duration of contact between the fatty material and the phosphoruspentoxide. In general, each of these four factors stands in reciprocalrelation to the other two, that is to say, other things being equal, thegreater the proportion of phosphorus pentoxide, the shorter the time ofcontact and/or the lower the temperature of reaction required to obtaina given result. Similarly, if the phosphorus pentoxide is relativelyvery finely divided, the amount thereof, the time and temperature ofheating may all be reduced. Or, to state another reciprocal relation,the higher the temperature of reaction, other things being equal, thecoarser may be the P205, the shorter the duration of contact and/or thelower the proportion of phosphorus pentoxide required to obtain a givenresult.

However, these reciprocal relations are valid only within certainreasonable limits. For example, while at temperatures below 105 C. somereaction does occur, it is very slow, so that to get appreciableinterface modifying potency in the product, the time of contact would beso long and the proportion of' phosphorus pentoxide required so high asto make such a procedure extremely inconvenient, in many instances. 1

On the other hand, the employment of temperatures substantially higherthan C. in general tends to reduce the potency of the product anddiscolor and char it, especially so when higher proportions ofphosphorus pentoxide or longer times of contact are employed. Thetemperature factor is particularly important in relation to thephosphorus pentoxide reaction because of the fact that this reaction isdecidedly exothermic. It is evident, therefore, that while considerablelatitude is permissible in the proportion of phosphorus pentoxide, inthe temperature range of the reaction, and in the time of contact ofphosphorus pentoxide with fatty material, certain criteria as to theinter-relationship of these three factors must be observed to securehigh interface modifying potencies in the product obtained.

Notwithstanding this, however, even though the reaction be subjected toconsiderable, even indiscriminate, variation in the three factorsindicated, the products obtained will still possess interface modifyingproperties such as those described herein. To be sure, in order toobtain high or outstanding potency with respect to such 'in fats.

$2,025,986v it interface modifying properties, those skilled in the artwill appreciate the importance of carefully adjusting the conditions ofthe reaction, particularly with respect to the three factors designated;An illustration of such preferred conditions is carefully specifiedhereina'bove in Example A. In all cases, however, the products obtainedcomprise esters of phosphoric acid interfacially active in fattycompositions falling into the class with which the present inventiondeals and the determinants of which are referred to at various points ofthis specification.

Erample Cocoa butteris treated by the same procedure,

with the same proportions successively of glycerine and phosphoruspentoxide and other materials, and under the same conditions oftirne,temperatures and stirringas described in Example A hereinabove. Theproduct obtained consists primarily of esters of phosphoric acid,somewhat firmer in texture and darker in color than the product obtainedin Example A, but has substantially the same interface modifyingproperties.

In practice I carry out my invention by taking the resultant phosphoruspentoxide reaction product of Example A and combining /a% on the basisof the fat used in the chocolate mix, together with the otheringredients, preferably by first melting the interface modifier withthefat into a homogeneous dispersion. Smaller pro,- portions such as,.for example, of a good,

' potent product as in Example A, may be used to obtain reduction inviscosity and a saving in the fat in the chocolate mix. Largerproportions may be used, if desired, as highas 1% or higher, however, issufiicient from a practical standpoint.

I may also disperse larger proportions of the phosphoric acid estersprepared as shown above persion of 50% of the phosphoric acid reactionproduct with 50%. of cocoa butter or hydrogenated fat or cocoanutstearine and vend same as such. A proportionate amount of this fattycomposition may be used to introduce ina chocolate mix to improve thechocolate mix by reducing its viscosity at desirable temperatures, asshown by the above examples.

In place of neutralizing the reaction mixture with sodium hydroxide, Imay neutralize it with other alkalis, such as for example, lime,anhydrous sodium carbonate or ammonia gas. In this case, the phosphoricacid ester of the glyceride used in this invention will not contain anynitrogen attachedto carbon, but the nitrogen of the ammonia will beattached to the phosphorus through oxygen.

In Example A or Example B given above, larger percentages of phosphoruspe'ntoxide may be used, such as 25% on the basis of the glyceride and avery good, potent product will be obtained under the conditionsspecified. On the other hand, as low as 1% of phosphorus pentoxide maybe used to react, .but higher temperatures will be necessary in order toobtain a product of some potency.

In neutralizing the ester with the sodium hydroxide solution, theresultant product will contain small amounts of moisture, from about 2%to 5%, depending upon the amount of moisture introduced by the solutionof the alkali.

Thus for example I may make a dis- Example 0 100 parts'of oleic acid(commercially pure) of good color, odor and taste, are heated with 100parts of glycerine (U. S. Pharmacopoeia grade) to 220 C. with stirringin an inert, that is, nonoxidizing, atmosphere, and the mixture ismaintained at this temperature with continuous stirring, in an inertatmosphere, for approximately two hours, until the free fatty acidcontent of the oil is about or less. The mixture is now allowed toremain at rest and to cool in an inert atmosphere and the excess ofglycerine is drawn off from the supernatant layer. I

71 parts of the supernatant layer and 56 parts of oleic acid(commercially pure) are heated with stirring at a temperature of 240 to250 C., (substantially dry, inert gas being vigorously bubbled throughthe mixture simultaneously),

for approximately four hours, until the free fatty acid content ofthe'mixture is approximately of 1% or less. The product is now cooled inan inert atmosphere.

100'parts of this product, which consists essentially of a mixture ofdiglycerides, dissolved in 300 parts of isopropyl ether, are refluxedfor two hours with 25 parts of finely divided phosphorus pentoxide, carebeing taken to exclude moisture from contaminating the reaction mixture.

The mixture is cooled; insoluble material is filtered off, the other isevaporated off and the product, which. consists essentially of esters ofphosphoric acid, may be used as such or it may be neutralized withalkaline agents such as sodium hydroxide, sodium carbonate, or the like.

Modified glycerides,for purposes of reaction with phosphorus pentoxide,in order to secure interfacially active esters of phosphoric acid forthe purposes of, my invention, may be obtained not only from the oilsand fats mentioned in Examples A, B and C, hereinabove, but also by themethods described in the aforementionedv examples and by other methods,from fatty materials such as corn oil, sesame oil, sunflower oil, lard,beef tallow, mutton tallow, h drogenated cottonseed oils and otherhydrogena ed oils and fats, peanut oil, palm oil, mixed fatty acids ob-.

tained by hydrolysis of fats and oils mentioned herein, commercialstearic acid, palmitic acid,

melissic acid, capryllic acid, lauric acid, myristic acid, oleic acid,cerotic acid and other fatty materials capable of reacting withglycerine and other polyhydric alcohols. v

Example D parts of finely divided phosphorus pentoxide are stirred intoa solution of parts of monophoric acid. in the form of a white,pulverizable solid with high potency with respect to the in erfaceproperties discussed hereinabove.

Many other more or less lipophile materials which have at least oneunesterifiedhydroxy group capable of reacting with phosphorus pen-- 4fiers by the methods described herein, particularly as in Example D, ingeneral, by causing approximately equal weights of phosphorus pentoxideto react with the organic substance in the presence of a solvent such asisopropyl ether. Other solvents may be used and the proportion ofphosphorus pentoxide is subject to considerable variation, subject tothe limitations discussed at great length thereinabove. In all casesinterfacially active esters of phosphoric acid possessing a lipophilegroup and a hydrophile phosphate group are obtained.

The physical properties of the product, such as color and consistency,depend a great deal upon the starting material. Melissyl alcohol, forexample, gives a rather hard, dark phosphate ester, whereas cetylalcohol produces a pasty material of a dark color. The solubility ordispersibility in oils and fats also varies with the relationship of thelipophile group to the hydrophile phosphate group. The more potentmaterials produce noticeable interfacial effects in proportions as smallas A; to Examples of the more or less lipophile materials possessing atleast one hydroxy group reactive to phosphorus pentoxide, which aresuitable for the purposes of my invention, in addition to those alreadymentioned herein, are as follows:

Hexyl alcohol, octyl alcohol, dodecyl alcohol, myristyl alcohol, oleylalcohol, octadecyl alcohol, ceryl alcohol, melissyl alcohol, castor oil,mono fatty acid esters of ethylene glycol, mono fatty acid esters of.diethylene glycol, mono fatty acid esters of glycerine, fatty acidesters of polyglycerols with at least one hydroxy group reactive tophosphorus pentoxide, cetyl glycerol ether,

lauryl ethylene glycol ether, myristyl diethylene glycol ether, otheralkyl ethcrs with at least one hydroxy group reactive to phosphoruspentoxide, and other more or less lipophile substances with at last onehydroxy group reactive to phosphorus pentoxide. All of these materialsgive reaction products with phosphorus pentoxide which comprise estersof phosphoric acid having a lipophile portion and a hydrophile phosphateportion and with marked interfacial activity of the kind discussed atgreat length hereinabove, making them very valuable as addition agentsin confections and the like.

My interface modifiers may be dried or further purified, decolorized ordeodorized, or diluted by incorporation of oils or fats, or otherwisetreated. The neutralization of the reaction products of my invention ingeneral seems to impart definite improvements in potency, stability,color, consistency, etc. The unneutralized product, sometimes of a darkbrown color, becomes lighter when treated with a neutralizing agent, adark brown product usually attaining a straw color. Indeed, the colormay be taken as an index in carrying out the neutralizing step. Usuallythe product particularly for water in oil emulsions and in many cases,to varying extents, they possess antispattering functions of the kinddescribed'at great length in United States Patent No. 1,917,256. readilyin oils, fats, waxes and other fatty materials, particularly when thetemperature is properly selected with cognizance of the melting pointThese interface modifiers disperseof the interface modifier as well asthe melting point of the fatty material in which it is to bedistributed.

As one example of the advantages to be obtained from the use of myinvention, a conventional chocolate mix may be considered. 100 c. c. ofa given chocolate mix composition was found to require about 85secondsat 43 C. to flow through a given orifice. In making a test of thischaracter, the mix is milled warm according to the usual custom forabout 15 minutes and then allowed to cool down to about 43 C., at whichtemperature the test is made. About 4% of one of the materials of myinvention, when added to such a mix and thoroughly dispersedtherethrough, will reduce the time of flow to 45 seconds, all conditionsremaining the same.

This reduction of viscosity, of course, may be taken advantage of invarious ways and may also be employed for the purpose of economizing inthe proportion of fat required. That is to say, a given viscosity may beobtained, other things being equal, with a substantially smallerproportion of fat ingredient.

The most desirable manner of incorporating the interface modifiers of myinvention isto dissolve'them in the fat content of the confection inwhich they are to be used. The usual fats employed are cocoa butter,so-called pressed butters. cocoanut stearine, palm kernel oil stearine,dairy butter, hydrogenated oils and other oils, fats and fattymaterials.

The invention has been considered from the standpoint of reduction inviscosity, but many ibility in enrobing temperatures; they make possiblelonger= cooling periods, thereby permitting longer time in tunnels;greater range of working temperatures on the enrobing machine ispossible; tempering is more uniform and gradual; in the cooking oftoffees, by virtue of the fact that a far superior and a much morestable emulsion is obtained, thev cooking is more flex- :ble andtolerates considerably more abuse and variation than heretofore,-withoutdetrimental effects on the ultimate product; the tendency to blooming isconsiderably'diminished and delayed. In many instances additionaldesired characteristics inure to the products concerned, by virtue ofthe diminished fat content.

A valuable feature of many of the products of my present invention isthat they can be produced in the form, of a substantially impalpablepowder, and are therefore conveniently and readily incorporated intoproducts of the character described. For example, many of the productsof my invention may be sprayed into a cold atmosphere whereby the finelydivided material of the spray is congealed and takes substantially apowder-like form. Still other ways of producing the substances in aconvenient and desirable condition for use may be employed.

According to the present improvements, any of my reaction productsproduced by methods illustrated in Examples A to D, inclusive, may beincreased in potency and generally improved for the purpose intended bythe use of a pretreat ment step prior to the formation of the ester. Inthis pretreatment step prior to the final esterification of the hydroxygroup or groups to form the phosphoric acid ester, a lipophile hydroxysubstance is treated with an agent capable of furnishing the elements ofphosphorus acids or capable of forming esters of phosphorus acids, forexample phosphorus pentoxide, phosphorus trioxide, or the like, thepretreatment step being carried on at a somewhat higher temperature thanthe temperature at whichthe final esterification takes place. Ingeneral, a very suitable agent'for use in the pretreatment step isphosphorus pentoxide. The pretreating agent, or its altered form,preferably is removed from the reaction product by suitable means suchas filtering, centrifuging and the like before the final esterificationstep. products of my copending application, Serial No.

710,893, results, however, even though the pretreatment agent be notremoved. In general, however, if the pretreating agent be not removedbefore the final esteriiying step, a greater Example E As anillustration of the process employing the pretreatment step, 600 poundsof cottonseed oil, hydrogenated to an iodine value of about 69, andpounds of cottonseed oil are heated together with 250 pounds ofglycerine to a. temperature of about 200 with constant stirring andpreferably in the presence of an inert atmosphere. 12 ounces of sodiumhydroxide flakes are added and the temperature raised to about 485 F.and held at that temperature for about two hours with constant stirring.The inert atmosphere may be maintained and stirring accomplished bybubbling the inert gas, such as carbon dioxide,

through the reaction mixture, but generally, when processing relativelylarge batches, mechanical stirring should be employed. In general, theproduct should be kept out of contact with atmospheric air at alltemperatures in the region of 200 F. and above. tions given, a productconsisting essentially of a mixture of mono-glycerides with some di-glycerides is produced, some free unreacted glycerine remaining. Thisglycerine may be removed by a lowing it to settle out, by centrifugingand the like.

In the pretreatment step 700 pounds of the esterified product producedas described directly hereinabove, are transferred to a jacketed kettle.

Approximately 75 pounds of finely divided phosphorus pentoxide are addedat a temperature of about 160 F., thorough agitation being continuous.The temperature rises to about 200 to 210 F. Steam is then circulated inthe jacket to raise the temperature to about 240 F. and the mixture ismaintained at that temperature. with c:n stant agitation for one-halfhour.. The reaction. product is then centrifuged to remove thephosphorus pentoxide and adhering organic matter. With the proportionsgiven, about 150 pounds'of a very viscous brown mass is centrifuged out.A clear liquid results from the re. moval of the phosphorus pentoxideand adhering organic matter andthis clear liquid may then be treatedfurther to form the phosphoric acid ester.

Marked improvement over the kettle and the half remaining in the kettleis Under the condi- The clear liquid obtained from the pretreatment stepis transferred back to the kettle and cooled to about F. 75 pounds offinely divided phosphorus pentoxide are then added with agitation. Atthe same time, cold water is cir-' 5' culated in the jacket. Thetemperature rises to about 180 to 190 F. in about five to ten minutesand remains at this temperature for several minutes and then begins tocool. It is allowed to cool to about 150 F. The total time required fromthe time the phosphorus pentoxide is added to the time it reaches itsmaximum temperature and then cooled to about 150 F. is about onehalfhour. This is found to give the best results when finely dividedphosphorus pentoxide is used. If coarse phosphorus pentoxide is used, itis added at about F. and the temperature rises alowly to 210 F. in abouttwenty minutes. At this point there is a tendency rorthe temperature torise, but this rise is checked by circulating cool water 20 in thejacket. The maximum temperature obtained'in this way is approximately214 to 215 F. The reaction mixture is allowed to remain at thistemperature for several minutes and is then allowed to cool to about 150F. This takes approximately another twenty minutes. A dark,reddish-brown viscous liquid is obtained.

In neutralizing the product, approximately onehalf of the reactionproduct is removed from the 30 cooled to about 120 F. 40 pounds offinely (iivided anhydrous sodium carbonate are then added at one timewith continuous agitation. The temperature may rise of itself as high asto F. over a period of about one-half hour. The cool- 3 ing water shouldbe circulated, if necessar n'to avoid further rise in temperature. inmost cases, the temperature will rise only to about iii-0 l t, but someapplication or" heat is advisable to raise the temperature to about 168l t, the tempera ed ture being maintained at this point for about onehalf hour, continuous agitation being employed. During the neutralizingstep, there is considerable eifervescence but it is not as copious,violent. or troublesome when the pretreatment step is employed as whenthe pretreatment step is omitted. After the product has been allowed toremain in the kettle with agitation for about one-halt hour at atemperature of 168 F., it is immediately centrifuged to remove excesssodium'carbonate 50 present. 1 v

The product resulting from this example is very valuable as a viscosityreducing agent in confections, particularly of the chocolate coatingtype. Other improvements are imparted tothe product 55 by thepretreatment step, however, and the prodnot is generally superior forsubstantially all types of confections of the general classes pointedout.

Example F 700 pounds of the esterified product produced in the firststep of Example E are transferred to a jacketed kettle and approximatelyW5 pounds of finely divided phosphorus pentoxide are added 65 at about160 F. with agitation. The temperature is permitted torise to about 200to 210 F. and then steam is circulated in the jacket to cause a furtherrise in temperature to about 240 F., this temperature being maintainedfor one-half hour 7 and the mixture being continually agitated. Theproduct is then centrifuged to remove insoluble material, apparentlyphosphorus pentoxide with some adhering matter.

The clear liquid is transferred back to the 7 kettle and cooled to about155 F. 75 pounds of finely divided phosphorus pentoxide is then addedwith agitation, cold water at the same time being circulated in thejacket. The temperature rises to about 180 to 190 F. in about five orten minutes and remains at this temperature for several minutes and thenbegins to cool. The total time required from the time the phosphoruspentoxide is added until the product has cooled to a temperature ofabout 150 F. is about one-half hour. Very good results are obtained bythis method when finely divided phosphorus pentoxide is employed. Ifcoarse phosphorus pentoxide is used, the temperature is somewhat higherand the time of heating is increased.

The product produced by esterification with the fine phosphoruspentoxide may be neutralized with dry ammonia gas in the followingmanner:

Dry gaseous ammonia is bubbled into 300 pounds of the phosphoric acidester, preferably in the form of fine bubbles, with vigorous stirringand with temperature control so as to maintain the entire mass at about130 F. The time required for neutralization is somewhat longer than whensodium carbonate is employed. The ammonia is continually passed throughthe product until a sample portion indicates that approximatelythree-fourths of the ammonia required to completely neutralize thephosphoric acid ester to phenolphthalein has been absorbed.

The ammonia salt thus obtained is of a lighter color than the phosphoricacid ester from which it is prepared, and is appreciably more potent inreducing the viscosity of the chocolate compositions thanthecorresponding sodium salt described in Example E.

The neutralization with the ammonia gas may becarried on at a lowertemperature or the time for neutralization may be decreased, if desired,by employing pressure, the ammonia gas, for example, being pumped intothe phosphoric acid ester under pressure, preferably with stirring.

Example G Substantially water free glycerine is polymerized, preferablywith the aid of an alkali catalyst,

until it has an average molecular weight corre-- of contact with themixture, preferably by maintaining an atmosphere of an inert gas at thesurface, for example by bubbling carbon dioxide through the mixturecontinuously. The reaction should be allowed to continue until theacidity of the mixture is below 1%, the time, temperature and conditionsdescribed usually being suitable to produce this result. The product isthen allowed to stand and any unreacted polyglycerol present is allowedto settle out.

To 450 parts of the mixed polyglycerol esters prepared as in thepreceding paragraph, while at a temperature of approximately 60 C., 75to 100 parts of fine phosphorus pentoxide are slowly added. A jacketedvessel may be employed to control temperature. The product is heated toapproximately 120 C. and kept at that temperature for about twentyminutes. It is then removed from the vessel and centrifuged to removeinsoluble materials, consisting for the most part of phosphoruspentoxide and adhering or loosely, combined organic matter.

400 parts of the pretreated product are returned to the jacketed vesseland at 50 C. fifty parts of fine phosphorus pentoxide are added 5 slowlythereto. The reaction mixture is heated to about 70 C. and thetemperature then rises to about 95 C. The product is kept at thistemperature for a few minutes, the total time for the entireesterification step being about twentyfive minutes.

The esterified product is neutralized suitably. either by the use ofsodium carbonate, as described in Example E, by the use of ammonia asdescribed in Example F, or by employing any other suitable alkalineorganic or inorganic neutralizing agent. In general, very good resultsare obtained if the hydrogen ions of the hydrophile phosphate group arereplaced by either sodium or ammonium ions.

It should be understood that the pretreatment conditions describedgenerally in the foregoing part of the specification and morespecifically in Examples E, F, andG hereinabove may be varied as totemperature, time, proportion.and kind of pretreating agent,-and foreach set of pretreating conditions, a corresponding potency is obtained.

In each of the examples given in which the pretreatment step isemployed, the pretreating agent, apparently in a somewhat altered form,is removed by centrifuging. Other adaptable'and' suitable methods ofremoval conventionally employed in the-chemical industries forseparation processes may be used. Moreover, the pretreating agent, suchas phosphorus pentoxidamay be allowed to remain. I have found, however,that even when phosphorus pentoxide is used for the pretreating step andalso for the final esterification step, more phosphorus pentoxide isrequired 40 in the esterification step if the phosphorous pentoxide usedin the pretreatment step be not removed. Furthermore, a highertemperature must be employed in the final esterification step. While theresulting product may have more potency than a product produced withoutthe use of the pretreatment step, such product, however, is not aspotent by any means as the product produced when the pretreating agentis removed after the pretreating step. 50.

Throughout this specification, I have employed the term lipophile todesignate organic rad cals with fatty characteristics. In general, suchradicals consist primarily of carbon and hydrogen, although they mayinclude other and/or ester linkages. I have employed this term lipophileto denote that the radical so designated has a distinct affinity foroils, fats, waxes and other fatty materials, and imparts a tendency tothe molecule of which it is a part, to be wetted by fatty materials.

I have employed the term hydrophile throughout this specificationprimarily to denote properties antithetical to the lipophile. Incounter-distinction to the lipophile radicals, the hydrophile radicalsconsist primarily of hydrogen and oxygen and the hydrophilecharacteristics are imparted primarily by hydroxy groups attached tocarbon or phosphorus. The hydrophillic character manifests itself by anaffinity for water and aqueous media, and the hydrophile radical impartsto the molecule of which it is a member, a tendency to be wetted bywater and aqueous media. The degree or extent of the hydrophilliccharacter is dependent upon the number of hydroxy groups and theirlocation in the molecule, and is also influenced by the number andcharacter of lipophile groups with which they are associated in themolecule.

- In considering the hydrophillic phosphate group, it is understood thatthe hydrogen ion of the phosphate hydroxy groups may be replaced byother cations, to form salts resulting from neutralization with organicor inorganic neutralizing agents. The product made by the methodinvolving the pretreatment step may, of course, be neutralized in thesame way as the product not made with the pretreatment step. Similarly,any of the lipophile materials of the character set out having anesterifiable hydroxy group may be employed with any of the methodsdescribed or modifications thereof.

What I claim as new and desire to protect by Letters Patent of theUnited States is:

l. A confection composition comprising comminutod material dispersed ina fat and including a proportion of a material comprising an ester of aphosphoric acid, said materia formed by pretreating a lipophile materialhavingat least one free hydroxy group with a derivative of.phosphoruscapable of forming an ester of phosphoric acid, and thereafterintroducing an additional amount of a derivative of phosphorus capableof forming ester of phosphoric acid, and reacting the resulting mixtureto produce an ester having a hydrophile phosphate group but devoid ofnitrogen directly linked to carbon.

2. A confection composition comprising comminuted material dispersed ina fat and including a proportion of a material comprising an ester of aphosphoric acid, said material formed 'by pretreating a lipophilematerial having at least one free hydroxy group with a derivative ofphosphorus capable of forming an ester of phosphoric acid, andthereafter introducing an additional amount of a derivative ofphosphorus capable of forming an ester of phosphoric acid, reacting theresulting mixture to produce an ester having a hydrophile phosphategroup but devoid of nitrogen directly linked to carbon, and neutralizingthe resulting product.

3. A confection composition comprising comminuted material dispersed ina fat and including a proportion of a material comprising an ester of aphosphoric acid, said material formed by pretreating a lipophilematerial having at least one free hydroxy group with aderivative ofphosphorus capable of forming an ester of phosphoric acid, removing saidderivative of phosphorus, and thereafter introducing an additionalamount of a derivative of phosphorus capable of forming an ester ofphosphoric acid, and reacting the resulting mixture toproduce an esterhaving a hydrophillic phosphate group but devoid of nitrogen directlylinked to carbon.

4. A confection composition comprising a comminuted material dispersedin a fat and including a proportion of a material comprising an ester ofa phosphoric acid, said material formed by pretreating a lipophilematerial having at least one free hydroxy group with a derivative ofphosphorus capable of forming an ester of phosphoric acid, removing saidderivative of phosphorus, and thereafter introducing an additionalamount of a derivative of phosphorus capable of formingan ester ofphosphoric acid, reacting the resulting mixture to produce an esterhaving a hydrophile phosphate group but devoid of nitrogen directlylinked to carbon, and neutralizing the resulting product.

5...A confection composition comprising comvminuted material dispersedin a fat and includ- 6. A confection composition comprising comminutedmaterial dispersed in a fat and including a proportion of a materialcomprisinga'n ester of a phosphoric acid, said material formed bypretreating a lipophile material having. at least one free hydroxy groupwith a derivative of phosphorus capable .of forming an ester ofphosphoric acid, substantially removing insoluble material from thereaction mixture, reacting the same with a derivative of phosphoruscapable of producing a phosphoric acid'ester, and neutralizing theresulting product.

7. A confection composition comprising comminuted material dispersed ina fat and including a proportion of a material comprising an ester of aphosphoric acid, said material formed by pre treating a lipophilematerial having at least one free hydroxy group with phosphoruspentoxide, and reacting the resulting material with a derivative ofphosphorus capable of forming an ester of phosphoric acid.

8. A confection composition comprising comminuted material dispersed ina fat andincluding a proportion of a material comprising arr-ester of aphosphoric acid, said material formed by pretreating a lipophilematerial having at least one free hydroxy group with phosphoruspentoxide, reacting the resulting material with a derivative ofphosphorus capable of forming an ester of phosphoric acid, andneutralizing the resulting product.

9. A confection composition comprising comminuted material dispersed ina fat and including a proportion of a material comprising an ester of aphosphoric acid, said material formed by pretreating a lipophilematerial having at least one free hydroxy group with phosphoruspentoxide, removing the phosphorus pentoxide, and reacting the resultingmaterial with a derivative of phosphorus capableof forming an ester ofphosphoric acid.

10. A confcc';ion composition comprising com minuted material dispersedin a fat and includinga proportion of a material comprising an ester 7sulting material with a derivative of phosphorus capable of forming anester of phosphoric acid.

11. A confection composition comprising a comrninuted niatcria includingsugar dispersed in a fat and having included therein a higher molecularweight ester of phosphoric acid with a l pophile radical and at leastone hydrophile phosphate group, prepared by pretreating a lipophilematerial having at least one free hydroxy group with phosphoruspentoxide before the formation of the phosphoric acid ester and reactingthe resulting product with a substance capable of forming an ester ofphosphoric acid.

12. A confection including fat, sugar and an ester of phosphoric acidformed by a process including pretreating a lipophile material having atleast one free hydroxy group with phosphorus pentoxide, and thereafterreacting the pretreated material with phosphorus pentoxide to form anester of phosphoric acid having a hydrophile phosphate group.

13. A confection including fat, sugar and an ester of phosphoric acidformed by a process includin pretreating a lipophile material having atleast one free hydroxy group with phosphorus pentoxide, and thereafterreacting the pretreated material With phosphorus pentoxide to form anester of phosphoric acid having a hydrophile phosphate group, andneutralizing the resulting product with ammonia.

1 1. The method of improving confections of a class including a ,fatwith comminuted material dispersed therein, which comprises pretreatinga lipophile material having at least one free hydroxy group with aderivative of phosphorus capable of producing an ester of phosphoricacid, reacting the pretreated material with a derivative of phosphoruscapable of forming an ester of phosphoric acid, and dispersing aproportion of the resulting material in the confection.

15. The method of improving confections of a class including a fat withcomminuted material dispersed therein, which comprises pretreating alipophile material having at least one free hydroxy group withphosphorus pentoxide,.reacting the pretreated material with a derivativeof phosphorus capable of forming an ester of phosphoric acid underconditions to produce an ester having a hydrophillic hosphate group, anddispersing a proportion of the resulting ester in said confection.

16. The method of improving confections of a class including a fat and asugar, which comprises pretreating a lipophile material having at leastone free hydroxy group with phosphorus pentoxide, removing thephosphoruspentoxide, reacting said material with a derivative of phosphoruspentoxide, neutralizing the resulting product with ammonia, anddispersing a proportion of the neutralized product in said confection.

17. The method of improving compositions of matter of a class consistingof chocolate-like coatin s for confections, including candy creams,cookies and ice cream, chocolate confections, icings, fillings; fudges,butter creams, caramels and toifees, which comprises dispersing in saidcompositions a proportion of an ester of phosphoric acid in the form ofa reaction product of phosphorus pentoxide and a lipophile molecule withat least one hydroxy group reactive to phosphorus pentoxide, and inwhich the esterified phosphate group is hydrophillic in character, and

neutralizing saidphosphate group, said ester being formed by firstpretreating said lipophile molecule with phosphorus pentoxide, and thenreacting the resulting pretreated product with acid, with a derivativeof phosphorus capable of forming an ester of phosphoric acid, andsubsequently introducing an additional amount of a derivative ofphosphorus capable of forming an ester of phosphoric acid, and reactingthe result- 5 ing mixture to produce a phosphoric acid ester devoid ofnitrogen linked directly to carbon.

19. A confection composition comprising comminuted material dispersed ina fat and including an ester. of phosphoric acid having lipophile andhydrophile groups prepared by pretreating a liquid vegetable oil fattyacid ester of glycerine with at least one free hydroxy group with aderivative of phosphorus capable of forming an ester of phosphoric acid,subsequently introducing an additional amount ofa derivative ofphosphorus capable of forming an ester of phosphoric acid and-reactingthe resulting mixture to produce an ester devoid of nitrogen linkeddirectly to carbon.

20. A confection composition comprising comminuted material dispersed ina fat and having including therein a phosphoric acid ester withlipophile and hydrophile groups, said ester prepared by treatingglycerin partially esterified with a high molecular weight unsaturatedfatty acid, witha derivative of phosphorus capable of forming an esterof phosphoric acid, and thereafter reacting the resulting product with aderivative of phosphorus capable of forming an ester of phosphoric toform a non-nitrogenous phosphoric acid ester.

21. A chocolate composition comprising sugar, chocolate and fat and anon-nitrogenous phosphoric acid ester having lipophile and hydrophilegroups, said ester prepared by pretreating with a derivative ofphosphorus capable of formingan ester of phosphoric acid, a higher fattyacid ester of glycerin with at least one free glycerine hydroxy group,and then reacting the resulting 40 I pretreated product with aderivative of phosphorus capable of forming an ester of phosphoric 1acid.

22. A chocolate composition comprising sugar, chocolate and fat and anon-nitrogenous phosphoric acid ester having lipophile and hydrophilegroups, said ester prepared by pretreating with a derivative ofphosphorus capable of forming an ester of phosphoric acid, anunsaturated higher fatty acid ester of glycerin with at least one freeglycerin hydroxy group, and then reacting the resulting pretreatedproduct with a derivative of phosphorus capable of forming an ester ofphosphoric acid.

23. A confection composition comprising com- I minuted materialdispersed in a fat and including an ester of phosphoric acid havinglipophile and hydrophile phosphate groups prepared by pretreating withphosphoruspentoxide a higher fatty acid ester of glycerine having atleast one 0 free glycerine hydroxy group, removing the phosphoruspentoxide and adhering organic matter, reacting the resulting pretreatedproduct with phosphorus pentoxide, and treating the reacted product witha neutralizing agent to decrease the acidity of the ester.

BENJAMIN R. HARRIS. v

